Use of n-aryl-n-substituted amino phthalamides as herbicides



United States Patent 3 549 34s USE OF N-ARYL-bl-SUBSTITUTED AMINO PHTHALAMIDES AS HERBICIDES Patented Dec. 22, 1970 The compounds of the present invention may be represented by the general formula:

Arthur H. Gevirtz, Orange, N.J., Ronald B. Ames, Nangafi tuck, and Allen E. Smith, Bethany, Conn., assignors to C-NHAr Uniroyal Inc., New York, N.Y., a corporation of New 5 Jersey CNHN-R1 No Drawing. Original application Oct. 20, 1967, Ser. No. 1 I

676,695, now Patent No. 3,502,685, dated Mar. 24, 0 R1 1970- Divided and this application Allg- 1969, where Ar is naphthyl, particularly a-naphthyl, the chloro- 847,706 substituted phenyls, such as diand trichlorophenyl, and U S C] 9/20 16 Claims R and R may be hydrogen or lower alkyl having 1 to 5 carbon atoms or compositely form a non-aromatic heterocycle, or if R is hydrogen, R is phenyl or naphthyl or chlorosubstituted derivatives thereof. Examples of R ABSTRACT OF DISCLOSURE and R are methyl, isopropyl, butyl, (CH CH O, Chemlcal Compounds havlng the gener in formula tetramethylene, pentamethylene, or hexamethylene.

0 The aforesaid compounds are prepared by reaction of g N-arylphthalimides with l to 2 equivalents of the de- NH-Ar sired hydrazine according to procedures known to those 20 experienced in the art. The reaction may be carried out C-NHN-R1 using an inert solvent such as water, methanol, acetonitrile as a reaction medium. The reaction can be carried out at room or reflux temperatures depending upon the where Ar is a naphthyl or chlorosubstituted phenyl group; nature f h h d i 1 and 2 are hydrogen or a lower alkyl group of 5 The following example illustrates the preparation of compositely form a heterocyclic ring, or, when R is hyh compounds f h i i drogen, R is phenyl, naphthyl, or a chlorosubstituted EXAMPLE I derivative thereof are used as herbicides.

N-( l-naphthyl -N'- (amino )phthalamide 14 g. (0.057) N-(l-naphthyl)phthahm1de M.P. 184- RELATION To OTHER APPLICATION 185 were added to 300 ml. of acetonitrile and 28 g. This application is a division of our copending applica- (0.09 mole) of anhydrous hydrazine were added with tion Ser. No. 676,695 filed Oct. 20, 1967, now U.S. Pat. stirring. Within 2 minutes new solid formation occurred. No. 3,502,685. The mixture was stirred one hour to insure complete re- This invention relates to N-aryl-N'-substituted amino action. Upon filtration 14.9 g. (96%) of white solid M.P. phthalamides and their use as herbicides, particularly, as 140-141 (dec.) were obtained. An infrared spectrum pre-emergent herbicides. showed the presence of moderate N-H bands at 3.08, 3.13

Controlling weeds in certain agricultural crops without and 3.21 1. and strong bands at 6.11, 6.22, 6.32 1. cominjuring the crop is a unique problem. Many herbicides 40 patible with the desired compound. will control weeds without injury only under optimum A representative list of compounds prepared by this conditions. Herbicides applied over a large geographical method and representative of the present invention are area seldom have optimum conditions to work. Under described in Table I.

TABLE I Calculated, percent Found, percent Empirical Ar R1 R2 M.P. formula C H N C H N 2,3-dich1orophenyl Methyl Methyl. Dec. 100 l-naphth do do 193-5 dee Do Hydrogen Hydrogen. 1401dec. ChaHtsNaOz 70.81 4.95 13.76 69.86 4. 93 14.3 Do do. Phenyl 214-5 dec 021112151 0 75.57 5.02 11.02 76.45 4.73 11. 30 Do Pentamethyle 205-6 11%.... 0231123560 73.97 6.21 11.25 73.60 6.22 11.82 1) (01 12o112)2o 217-8 deem. C24H1QN302 70. as 5.64 11.19 70. 53 5.65 11.57

0 3,5-dichlorophenyl- Hy drogen Hydrogen. 132-3 dec adverse conditions, such as heavy rainfalls or very dry soil conditions, pre-emergent herbicides will give erratic performance. N-l-naphthyl phthalamic acid, a well known pre-emergent herbicide, performs well under optimum conditions in that it controls weeds without injuring the crop. Under wet or heavy rainfall conditions, N-lnaphthyl phthalamic acid will move downward through the soil into the germinating crop seed zone and cause considerable injury. The present invention is unique in that, by converting the carboxyl group of N-l-naphthyl phthalamic acid to a hydrazide group, leaching is virtually eliminated. This is a desirable discovery for two reasons: firstly, the chemical stays in the germinating weed seed zone, facilitating weed control; and secondly, the chemical is less likely to injure the crop seed germination since this zone is below the weed seed zone. To initiate this activity, phthalamides may be applied to the soil at, before or after crop emergence and before weed emergence.

The chemicals of the present invention may be applied to soil at, before or after crop emergence and before weed emergence. The chemicals may be applied to soil in various forms as explained below.

The chemical may be impregnated or granular organic and inorganic carriers such as corncobs, activated carbon, attapulgite clay, mica and other types of granular carriers known in the art. They may also be pelletized as described by Gallaway Pat. No. 3,056,723 or by Polon Pat. No. 3,192,290. If desired, the chemicals may be mixed with a powdered solid carrier, together with a surface active dispersing agent, so that a wettable powder may 'be obtained which may be applied directly, or which may be shaken up with water to make an aqueous dispersion for application in that form. The chemicals may be dissolved in aliphatic and aromatic hydrocarbons, and the solution of the chemical dispersed in water with the aid of a surface-active dispersing agent to give a sprayable aqueous dispersion. Such surface-active dispersing agents may be anionic,nonionie or cationic surface active agents. Such surface-active agents are well known and reference is made to Hofiman et'al., U.S. Pat. No. 2,614,- 916, columns 2 to 4, for detailed examples of the same.

The chemicals, in the forms listed above, may be applied (1) to the surface and (2) to soil surface and incorporated to a depth of /2 to 2".

The chemicals may be applied to the soil at rates of 1 to 40 pounds/acre, preferably, up to 20 pounds/acre.

To illustrate more fully the herbicidal use of the compounds of the instant invention attention is directed to the following example:

EXAMPLE II One hundred and fifty mg. of each chemical were ground and blended with 75 mg. of a wettable powder containing 4% Triton X120 (alkylaryl polyether alcohol OPE9-10), 4% Daxad 11 (alkylnaphtholene sodium sulfonate) and 92% Dixie clay (inert).This mixture was made up to 300 ml. with H O, giving a 500 p.p.m. solution. Forty and eightly ml. of the 500 p.p.m. solution were made to 160 ml. with H O to give two solutions containing 125 and 250 p.p.m. solution respectively. Eighty mls. of each concentration were drenched on a 150 mm. pot which contained a mixture of four broadleaf weeds, namely pigweedAmaranthus retroflexus, purslanePortulaca oleracea, lambsquartersChenpodium album and oxeye daisyChrysanthemum leucanthemum. Also in the pot were three grass species, namely crabgrassDigitaria sanguinalis, barnyard grassEchinochlea crusgalli and giant foxtailSetaria faberii. Eighty ml. of the remaining concentrations were applied as replications. Eighty ml. of the three concentrations, 125, 250 and 500, as applied are equal to 5, and pounds per acre. Pots were subirrigated and scored 14 days later. Table II illustrates the herbicidal activity of the compounds of the invention:

TABLE II Percent control at- N-(l-aiaphthyl)-N-(dimethylamino)-phthala- N-(l-naph thyl) -N'-(amino) -ph thalamide 92 87 85 N-(l-naphth yl) -N-(anilin o) -phthalamide 96 89 U1 N-(l-naphthyl)-N-(piperidino) -phthalamide 73 80 50 N-(l-naphthyl)-N-(1norph0lin0)phthalamide. 94 84 60 N-(3,5-dichlorophcnyl)-N-(amino)jphthalamide Injury to the soybean plants was measured as percent stunting as compared to control as well as percent occurrence of negative geotropic type injury. Results are given in Table III:

TABLE III Percent control a.t-

20 lbs./ 101135.] 5 lbs./ A. A. A.

N-(laiaphthyD-N -(dimethylamino) phthalam e 5 5 N-(l-naphthyl) -N-(amino) phthalamide 0 0 0 N-(2,3-diohlorophenyl)-N-(dimethylamino)- phthalamide. 15 0 0 N-(l-naphthyDphthalamie acid 90 78 70 II G-NH-Ar where Ar is naphthyl, dichlorophenyl or trichlorophenyl and R and R are hydrogen or lower alkyl having from 1 to 5 carbon atoms or compositely form, with the N atom to which they are-bonded, a piperidino or a morpholino ring or, when R; is hydrogen, R is phenyl; and a surface active agent.

2. The herbicidal composition of claim 1 wherein Ar is u-naphthyl.

3. The herbicidal composition of claim 1 wherein the compound is N.-(l-naphthyl)-N'-(amino)phthalamide.

4. The herbicidal composition of claim 1 wherein the compound is N-(2,3-dichlorophenyl) -N'-(dimethylamino) phthalamide.

5. The herbicidal composition of claim 1 wherein the compound is N-( l-naphthyl) -N- (dimethylamino phthalamide.

6. The herbicidal composition of claim 1 wherein the compound is N-(1-naphthyl)-N-anilino)-phthalamide.

7. The herbicidal composition of claim 1 wherein the compound is N-(I naphthyl) N (piperidino) phthalamide.

8. A method of controlling weeds which comprises treating the soil with a herbicidally effective amount of from 1 to pounds per acre of a compound having the formula:

where Ar is naphthyl, dichlorophenyl or trichlorophenyl and R and R are hydrogen or lower alkyl having from 1 to 5 carbon atoms or compositely form, with the N atom to which they are bonded, a piperidino or a morpholino ring or, when R is hydrogen, R is phenyl.

9. The method of controlling weeds of claim 8 wherein Ar is a-naphthyl.

10. The method of controlling weeds of claim 8 wherein the compound is N-(l-naphthyl)-N-(amino)phthalamide.

11. The method of controlling weeds of claim 8 wherein the compound is N- (2,3-dichlorophenyl)-N-(dimethylamino) phthalamide.

12. The method of controlling weeds of claim 8 wherein the compound is N-(1-naphthyl)-N-(dimethylamino) phthalamide.

13. The method of controlling weeds of claim 8 wherein the compound is N-(1-naphthyl)-N'-(anilino)- phthalamide.

14. The method of controlling weeds of claim 8 wherein the compound is N-(1-naphthyl)N'-(piperidrno phthalamide.

15. The herbicidal composition of claim 1 wherein the compound is N- l-naphthyl) -N- (morpholino -phthalamide.

16. The method of controlling weeds of claim 8 wherein the compound is N-(l-naphthyl)-N'-(morpholino)-phthalamide.

References Cited UNITED STATES PATENTS JAMES O. IHOMAS, JR., Primary Examiner U.S. Cl. X.R. 71-94, 118 

